Mn 4 þ -activated fluoride compounds, as an alternative to commercial (oxy)nitride phosphors, are emerging as a new class of non-rare-earth red phosphors for high-efficacy warm white LEDs. Currently, it remains a challenge to synthesize these phosphors with high photoluminescence quantum yields through a convenient chemical route. Herein we propose a general but convenient strategy based on efficient cation exchange reaction, which had been originally regarded only effective in synthesizing nano-sized materials before, for the synthesis of Mn 4 þ -activated fluoride microcrystals such as K 2 TiF 6 , K 2 SiF 6 , NaGdF 4 and NaYF 4 . Particularly we achieve a photoluminescence quantum yield as high as 98% for K 2 TiF 6 :Mn 4 þ . By employing it as red phosphor, we fabricate a high-performance white LED with low correlated colour temperature (3,556 K), high-colour-rendering index (R a ¼ 81) and luminous efficacy of 116 lm W À 1 . These findings show great promise of K 2 TiF 6 :Mn 4 þ as a commercial red phosphor in warm white LEDs, and open up new avenues for the exploration of novel non-rare-earth red emitting phosphors.

Ultrasmall inorganic oxide nanoparticles doped with trivalent lanthanide ions (Ln(3+)), a new and huge family of luminescent bioprobes, remain nearly untouched. Currently it is a challenge to synthesize biocompatible ultrasmall oxide bioprobes. Herein, we report a new inorganic oxide bioprobe based on sub-5 nm amine-functionalized tetragonal ZrO(2)-Ln(3+) nanoparticles synthesized via a facile solvothermal method and ligand exchange. By utilizing the long-lived luminescence of Ln(3+), we demonstrate its application as a sensitive time-resolved fluorescence resonance energy transfer (FRET) bioprobe to detect avidin with a record-low detection limit of 3.0 nM. The oxide nanoparticles also exhibit specific recognition of cancer cells overexpressed with urokinase plasminogen activator receptor (uPAR, an important marker of tumor biology and metastasis) and thus may have great potentials in targeted bioimaging.

K2TiF6:Mn4+ is a highly efficient narrow‐band emission red phosphor with promising applications in white light‐emitting diodes (LEDs) and wide‐gamut displays. Nevertheless, the poor moisture‐resistant properties of this material hinder commercialization. A convenient reverse cation‐exchange strategy is introduced for constructing a core–shell‐structured K2TiF6:Mn4+@K2TiF6 phosphor. The outer K2TiF6 shell acts as a shield for preventing moisture in the air from hydrolyzing the internal MnF62− group, while effectively cutting off the path of energy migration to surface defects, thereby increasing the emission efficiency (especially for the phosphors doped with high concentrations of Mn4+). Employed as a red phosphor, the packaged white LED exhibits an extraordinarily high luminous efficacy of 162 lm W−1, a correlated color temperature (CCT) of 3510 K, and a color rendering index of 93 (Ra). Aging tests performed on this device at 85 °C and 85 % humidity for 480 h retain up to 89 % luminous efficacy. The findings could facilitate commercial application of K2TiF6:Mn4+@K2TiF6 phosphor.